Oxybromination of chlorodifluoromethane



United States Patent OXYBROMINATION OF CHLORODIFLUORO- METHANE Robert P. Ruh and Ralph A. Davis, Midland, Mich., as-

signors to The Dow Chemical Company, Midland, Mich., a corporation of Delaware No Drawing. Application February 16, 1955 Serial N0.'488',700

2 Claims. (Cl. 260-6533) This invention relates to the bromi'nation of chlorodifiuoromethane in the presence of oxygen, such reaction being referred to hereinafter as oxybromination.

It is known that polyhalomethanes containing at least one hydrogen atom and at least one fluorine atom in the molecule, e. g. difluoromethane, trifluoromethane, and chlorodifluoromethane, can be thermally brominated. The bromination of chlorodifluoromethane proceeds according to the following equation:

Such a thermal bromination is very ineflicient in the utilization of bromine, however, since for every atom of bromine replacing a hydrogen atom in the reactant polyhalomethane molecule, one atom of bromine is consumed in the formation of a molecule of by-product hydrogen bromide. I

It has now been found that when a mixture of bromine and oxygen is contacted with chlorodifluoromethane at an elevated temperature in the presence of a salt or an oxide of chromium as catalyst, an oxybromination reaction occurs in accordance with the following overall equation:

Under optimum reaction conditions, high conversions and yields of CBrClF are obtained with little if any formation of by-product hydrogen bromide. That this reaction will proceed at all is quite unexpected since, under similar conditions, both CH F and CHF decompose With the liberation of large quantities of hydrogen fluoride, practically no brominated products being formed.

According to the process of the present invention, a mixture of oxygen and bromine in a mole ratio of at least 0.5 :1 are heated together with chlorodifluoromethane to a reaction temperature above about 300 C. in the presence of a salt or oxide of chromium as a catalyst. This is conveniently carried out by passing a mixture of CHClF Br and 0 through a heated bed of the catalyst in any suitable reaction vessel.

The catalysts which are effective in the instant process are oxides and inorganic salts of chromium. These catalysts may be pelleted and employed per se. Ordinarily, however, they are prepared by treating a suitable support, such as alumina, calcium fluoride, or copper gauze, with an aqueous solution of an inorganic acid salt of the chromium, for example, the nitrate, sulfate,

chloride, or other halides, and then mildly heating to remove water, or heating at an elevated temperature to convert the salt to the oxide. In carrying out the instant process, the dry salt is sometimes transformed into the oxide or a halide, e. g. a fluoride. The preferred catalyst, however, is prepared from chromium salts, such as chromic nitrate, chromous chloride, and chromic sulfate. Chromic nitrate is especially desirable and is readily converted to chromium oxide, Cr O upon heating in the presence of oxygen, e. g. air.

The oxybromination of CHClFg to CBrClF is carried 2,871 ,Z74 Patented Jan. 27,- 1 959 out at a reaction temperature above 300 C. but below the temperature at which decomposition becomes pronounced as evidenced by the formation of hydrogen fluoride. ing to the reaction conditions, e. g. reactant ratio, contact time, etc. For all practical purposes, the reaction temperature can be restricted to the range of from-300 to 600 C., with a temperature in the range of from 400 to 550 C. ordinarily preferred for best results.

The temperature at which the oxybromination reaction is conducted governs to-a large extent the contactv time, i. e. residence time in the reaction zone. In ,general,.a sufficiently long time of contact is employed to effect the desired reaction at a given temperature, the contact time varying inversely as the temperature. For example, a contact time as long as 75 seconds may sometimes be employed at 300 C. At a temperature of 600 C., however, a contact time of only a fraction of a second may be used. Ordinarily, it is preferred to use a contact time of from 1 to 30 seconds.

For maximum conversion of CHClF to CBrClF it is desirable to employ CHCIF and Br in a reactant ratio closely approximating the stoichiometric proportion of 2:1. A mere trace of bromine, though efiective, is impractical, in the oxybromination reaction. Although excess bromine may be employed, a large excess of bromine over the stoichiometric proportion required to prepare CBrClF is unnecessary. In ordinary practice, from 0.25 to 0.5 of a mole of Br per mole of CHClF is employed in carrying out the instant process. With respect to the oxygen, at least 0.5 mole of 0 per mole of Br is generally used, good results being obtained when oxygen and bromine are employed in a mole ratio of greater than 4:1, e. g. when passing CHClF Br and O in a mole ratio of l.0:0.33:l.5 through a bed of a chromium oxide catalyst at a temperature of 500 C. Although substantially pure oxygen gas is generally preferred for use in the instant process, a gas containing molecular oxygen, e. g. air, may also be effectively employed.

The oxybromination process of the invention may be carried out either batchwise or continuously. Continuous operation is preferred both for ease in carrying out the process and because better yields result. A cylindrical reaction tube constructed of or lined with a material which is inert under the conditions of the reaction is a suitable reaction vessel for such operation.

The following example illustrates but does not limit Example A vapor-phase mixture of chlorodifluoromethane, bromine, and oxygen was passed into a three-quarter inch inside diameter vertical silica tube containing a 24 inch bed of catalyst consisting of Cr O supported on onequarter inch rings of aluminum silicate. The catalyst bed was externally heated and maintained at a temperature of 500 C. as measured by a thermocouple placed on the outside of the tube near the middle of the heated zone. The gaseous reactant mixture was formed by passing metered chlorodifluoromethane gas through liquid bromine in a glass vaporizer, the temperature being regulated to give the desired ratio of Br to CHCIFg. Just prior to entering the top of the reaction tube, metered oxygen gas was introduced into the mixture of bromine and chlorodifluoromethane. During a period of minutes, 1.39 moles (120 grams) of CI-ICIF 0.49 mole (78 grams) of Br and 0.54 mole of oxygen were passed through the reaction tube. This represents a molar reactant ratio of CHC1F :Br :O of 1.0: 0.35:0.39 and a contact time of 8.2 seconds. The eflluent gas stream was scrubbed with water and condensed in a receiver cooled This decomposition temperature varies accord-- in solid carbon dioxide. The total condensate weighing 175 grams was scrubbed with aqueous potassium iodide and titrated with standard sodium thiosulfate solution. The total inorganic bromine recovery was calculated to be 6.4 grams. Upon fractionally distilling the total organic product in a Podbielniak column, the overall recovery (based on the CHCIF charged) was 85.5 mole percent as follows:

Mole percent That'which is claimed is:

'1. A method of making CBrClF which comprises passing through a bed of a catalyst consisting essentially of chromic oxide at a reaction temperature in the range of from 300 C. to 600 C. and at a contact time of from 1'-to 75 seconds, a vapor phase mixture of Br CHClF and O in a mole ratio of Br to CHCIF of at least 0.25:1 and of O to Er of at least 0.5:1.

2. A method which comprises passing through a bed of catalyst consisting essentially of Cr O at a reaction temperature in the range of from 400 to 550 C. and at a contact time of about 1 to 30 seconds, a vapor-phase mixture of Br CHClF and O in a mole ratio of from 0:25 to 0.50 mole of Br per mole of cHClF- the mole ratio of O to Br; being from about 0.5:1 to about 1:1, and separating CBrClF from the resulting product mixture.

References Cited in the file of this patent UNITED STATES PATENTS 1,591,984 Krause et al July 13, 1926 2,284,482 Vaughn et al. -2 May 25, 1942 2,334,033 Riblett Nov. 9, 1943 2,379,414 Cass July 3, 1945 2,514,473 Chaney July 11, 1950 2,578,913 Whitman Dec. 18, 1951 FOREIGN PATENTS 108,424 Austria Dec. 27, 1927 1,078,266 France May 5, 1954 

1. A METHOD OF MAKING CBRCIF2 WHICH COMPRISES PASSING THROUGH A BED OF A CATALYST CONSISTING ESSENTIALLY OF CHROMIC OXIDE AT A REACTION TEMPERATURE IN THE RANGE OF FROM 300*C. TO 600*C. AND AT A CONTACT TIME OF FROM 1 TO 75 SECONDS, A VAPOR PHASE MIXTURE OF BR2, CHCIF2, AND O2 IN A MOLE RATIO OF BR2 TO CHCIF2 OF AT LEAST 0.25:1 AND OF O2 TO BR2 OF AT LEAST 0.5:1. 